Nitroaminobenzene ester compounds



Patented May 10, 1949 NIITED S TAT-ES PATENT OFFICE 2,469,695NITBOAMINOBENZENE ESTER COMPOUNDS James G,.M-cNally, Kingsport, Tenn,and Joseph B. Dickey, Rochester, N. Y., assignorsto EastmanKoda'kCompany, Rochester, N. Y., a corporation of N ew 'J ersey No Drawing.Application February 2, 1946, Serial No. 645,230

4-(Jlaims. (Cl. 260-490) This invention relates tomew non-sulfonatednitroaminobenzene ester compounds and their application to thear-t ofdyeing or coloring.

The compounds of our invention constitute waluable-dyes forthe'colora-tion of textile materialsprepared from organic-derivatives ofcellulose, wool, silk, nylon and Vinyon. They are alsousefulforthecoloration of lacquers made Irom or containing organic derivatives ofcellulose, and polymeric materials. prepared from compounds containingthe -C=C'- group. The compounds of our invention are especially suitedfor the coloration of, cellulose acetate textile materials.

We are aware that itis known to make nitroarylamine dye. compounds.However, so far as we are aware, the compounds of our invention arenovel and as they do not sublime they areiree lfrom one of: thedifflculties commonly encountered by dyers when attempting to. employthe known nitroarylaminedyesfor dyeing, Also the dyecompounds of ourinvention yield ,yellow shades which possess superior light ,fastnessproperties.- Further, they. have. good tinctorial power and are.readily: applied to the materials abovenamed.

The. new non-sulfonated nitroaminobenzene ester compounds of ourinvention have the gen- :eral formula:

.n v.n a-enx i-em V wherein .3 represents. a. mono snitratednonesulfonated monocycllc benzene nucleus which can have one\morecsubstituent other than an additional nitrov.,group or a sulfon'icacid. group, 13,731 and R2 each represent a member selected Irom thegroup consisting ,ot a low carbon alkyl group, apmethylol group, ..,a

group, a

group, and a -onro-- :o-a1k 1 group, and R1 maybe in addition hydrogenand wherein at least oneacizthe members R, R1 and R2 must be a memberselected from the group consisting of a -CHaO-%alkyl The newnon-sulfonated nitroaminobenzene ester compoundsof aourinvention can beprepared by treating the non-sulfonated nitroaminobenzene compoundshavingthe general formula:

3 have discovered that dyeings obtained with compounds wherein B has twonitro groups possess poor light fastness properties.

The compounds having the general formula:

can be prepared by reacting a monocyclic nonsulfonated mono nitrochlorobenzene which can have one more substituent, other than anadditional nitro group or a sulfonic acid group, with a primary aminehaving the formula:

X, X1, and X2 have the meaning previously assigned to them.

Primary amines of the formula x H2N( JXl include, for example,2-aminopropanediol-1,3

H2OH 2-amino-2-methyl propanediol-1,3

onion- [Hm-(LH,

(|)H2OH 2-amino-2-ethyl propanediol-1,3

CHZOH [H2N :-o=m

HzQ trimethylol methylamine [H2N-C (CHzOHhl 2-amino-2- (n-propyl)-propanediol-1,3

CHzOH 2-amino-2- (n-butyl) -propanediol-1,3; 2-methylol-n-butane andZ-amino-l-methylol-n-butane (EHQCH; [BUN-(EH CHzOH 2-aminochloro 1 nitro5 thiocyanobenzene, 5-acetamino 2 chloro 1 nitrobenzene, 2-chloro-5-hydroxy-l-nitrobenzene, 2 chloro -lnitro-5- sulfone-amidobenzene and2-chloro5-ethylsulfone-l-nitrobenzene.

Esterifying agents that can be employed in the preparation of thecompounds of our invention include, for example, acetic anhydride,propionic anhydride, butyric anhydride, valeric anhydride, n caproicanhydride, n caprylic anhydride, N-lauryl anhydride, acetyl chloride,n-propionyl chloride, n-butyryl chloride, isobutyryl chloride, n-valerylchloride, isovaleryl chloride, n-caproyl chloride, n-lauryl chloride,n-palmityl chloride, benzoic anhydride, benzoyl chloride, p-nitrobenzoylchloride, o-nitrobenzoyl chloride, mnitrobenzoyl chloride, o-toluylchloride, p-toluyl chloride, furoyl chloride, tetrahydrofuroyl chloride,,B-methoxyacetyl chloride (ClCDCHzOCHs), c-ethoxyacetyl chloride(CICOCHzOCzHs), ethyl chlorocarbonate (ethyl chloroformate), methylchloroformate and n propyl chloroformate (ClCOOCI-IzCHzCI-B) Thefollowing examples illustrate our new dye compounds and the manner oftheir preparation.

Example 1 19.2 grams of 2,5-dichloronitrobenzene, 50 cc. of butanol,10.5 grams of 2-amino-2-methy1propanediol-1,3 and 5.5 grams of sodiumcarbonate were placed in a suitable reaction vessel and refluxedtogether for 22-23 hours. The reaction mixture was then steam distilledand the distillate was cooled to room temperature and filtered. Threegrams of 5-chloro-2-(2-imino-2-methylpropanediol 1,3) 1 nitrobenzene,having the formula OHzOH H2OH N02 were obtained.

19.2 grams of 2,5-dichloronitrobenzene, 9.2 grams of sodium bicarbonate,10.9 grams of 2- amino-2-methylpropanediol-1,3 and 50 cc. of butanolwere placed in a suitable reaction vessel and refluxed together for 32hours. The reaction mixture was then steam distilled and the distillatewas cooled to room temperature and filtered. 2.9 grams of5-chloro-2-(2-amino-2- methylpropanedio1-1,3)-1-nitrobenzene wereobtained.

19.2 grams of 2,5-dichloronitrobenzene, 5.8 grams of sodium carbonate,10.9 grams of 2- amino-2-methylpropanediol-1,3 and 50 cc. of amylalcohol were placed in a suitable reaction vessel and refluxed togetherfor 12 hours. The reaction mixture was then steam distilled and thedistillate was cooled to room temperature and filtered. 1.5 grams of5-chloro-2-(2-imino-2- methyl-propanediol-l,3) 1 nitrobenzene wereobtained.

Seven grams of5-chloro-2-(2-imino-2-methylpropanediol-l,3)-1-nitrobenzene obtainedfrom the runs described above were dissolved in 25 cc. of boiling ethylalcohol and the resulting solution was filtered While hot and cooled toroom temperature to recrystallize the 5-chloro-2-(2-imino-2-methylpropanediol 1,3) 1 nitrobenzene. The first four gramscrystallizing out Were recovered and had a melting point of 161-- 164 C.

The four grams of 5-chloro-2-(2-imino-2- methyl-propanedi01-1,3) 1nitrobenzene, obs

areas-es taihedas described above, were placedin a s'uit able reactionvessel and heated for 1 /2 hours on an oil bath with cc. of glacialacetic acid and 1000. of acetic anhydride. The reaction mixtureresulting from this treatment was then poured into cold water toprecipitate the diacetic acid ester of 5-chloro-2- (2-iniino-2-methylpropanediol-1,3) l-nitrobenzene cin o-ccn3 which wasrecovered by filtration. Upon recrystallization from ethyl alcohol andwater a yield of..4.8 grams of the desired product, having a meltingpoint of 5'7-59 C. was obtained.

Example 2 13.2 grams of 2-chloro-5-N ethylsulfoneamide-l-nitrobenzene,5.2 grams of 2-amino- 2-methylpropanediol-1,3 and 2.8 grams of sodiumcarbonate were placed in a suitable reaction vessel and heated togetheron an oil bath for six hours at 170 C. Considerable foaming, indicatingreaction, took place during this heating. Ethyl alcoholwas' added to thereaction mixture to dissolve the2-'(2-imino-2-methylpropanedi'ol-L3)-5-N ethylsulfoneamide 1nitrobenzene formed in the reaction. The reaction mixture was thenpoured into cold dilute aqueous hydrochloric acid with stirring. Theyellow precipitate which formed was recovered by filtration and washedwith water. The yellow precipitate consisting essentially of2-(2-imino-2- methylpropanediol 1,3) 5N-ethylsulfoneamide-l-nitrobenzene became gummy on standing butcrystallized after standing over night.

The 2-(2-imino-2 methylpropanediol- 1,3) -5-N-ethyl-sulfoneamide-l-nitrobenzene obtained as described above, wasplaced in a suitable reaction vessel together with sufiicient aceticanhydride to acetylate the methylol groups and the reaction mixture washeated on a steam bath for two hours following which it was poured intoice water. The diacetic acid ester of 2-(2-imino-2-methylpropanedio1-L3) -5-N-etliylsulfoneamide 1 -nitrobenzene,

formed was recovered by filtration, washed with water and dried.

Example 3 is crystallized from ethyl alcohol. It colors celluloseacetate greenish-yellow shades.

The yellow product obtained thereby and.

Example 4 H sagas l nt-o-c-mcin, N02 1 is recovered by filtration,washed with water and dried.

Example 5 10 grams of 4'-(-2-iminop ropanediol-1,3)1-

nitrobenzene are placed in a suitable reaction vessel, cooled to 15 and0.2 gram molecular weight of acetic anhydride diluted with 25 cc. ofglacial acetic acid are added. If desired, a drop of-sulfuric acid maybe used as a catalyst. The reaction mixture is warmed slightly and thenpoured into water. A yellow solid having the formula:

is recovered by filtration, washed with water and dried. It may befurther purified by crystallization from ethyl alcohol if desired.

4 (2 iminop ropanediol L3)-1-nitrobenzene is, prepared by reacting onemolecular equivalent weight or p-nitrochlorcbenzene with two of 2-aminopropanediol -lfi in accordance with the general procedure indicatedhereinbe'fore.

Example 6 1-5.6 grams ofo-n-itrochlorobenzene, 12 grams".-

of trimethylol methylamine and 6 grams of sodium carbonate are placed ina suitable reaction vessel and heated at C. with stirring until no morecarbon dioxide is evolved. The reaction product is then poured intowaterand the reddish gummy solid that separates is recovered byfiltration and crystallized from a solvent such as ethyl alcohol,butanol, acetic acid "or 1,4-dioxane. 2-

(2-imihopropane'tri'ol-1,2,3) -1-nitrobenzene having the formula:

CHzOH H t N CH1OH is obtained.

The reaction product obtained as described above is dissolved inpyridineand treated with 3.5.1moleoularequivalents of b'enzoyl chloride at roomtemperature. The esterifi'cation reaction which takes place is completedby warming. The desired product having the formula:

qau cmos g is obtained on working up the reaction mixture in accordancewith the procedure described in Ex-.. ample 4.

Ewample 7 26 grams of 5-chloro-2-(2-iminopropanediol- 1,3)-l-nitrobenzene are dissolved in 200 grams of pyridine and 23 grams of,B-methoxyacetylchloride are added at room temperature. The reactionwhich takes place is completed by warming. Then enough aqueous sodiumbicarbonate solution is added to neutralize the hydrochloric acidpresent in the reaction mixture. The pyridine present in the reactionmixture is removed by distillation under reduced pressure (10 mm., forexample), water is added to the reaction mixture and the product havingthe formula:

is recovered by filtration, washed with water and dried.

Example 8 13.2 grams of 2-chloro-5-N-ethylsulfoneamidel-nitrobenzene, 6grams of trimethylol methylamine and 2.8 grams of sodium carbonate wereplaced in a suitable reaction vessel and heated together on an oil bathfor 6 hours at 170 C. Considerable foaming, indicating reaction, tookplace during this heating. Ethyl alcohol was added to the reactionmixture to dissolve the 2- 2 iminopropanetriol 1,2,3)--N-ethylsulfoneamide-l-nitrobenzene formed in the reaction. Thereaction mixture was then poured into cold dilute aqueous hydrochloricacid with stirring. The yellow precipitate which formed was recovered byfiltration and washed with water. The yellow precipitate consistingessentially of 2-(2- iminopropanetriol-1,2,3) -5 N ethyl sulfoneamide-l-nitrobenzene became gummy on standing but crystallized afterstanding over night.

The product obtained as described above was placed in a suitablereaction vessel together with suflicient acetic anhydride to acetylatethe methylol groups and. the reaction mixture was heated on a steam bathfor two hours following which it was poured into ice water. Theprecipitate formed was recovered by filtration, washed with water anddried. It has the formula:

O O I 0 and can be further purified by dissolving in ethyl alcohol andprecipitating by evaporation of the alcohol.

Example 9 This compound can be obtained by preparing the mono aceticester of 2-(2-imino-2-methylpropanediol-1,3)-1-nitrobenzene inaccordance with the general procedure described in Example 3 andtreating the mono acetic ester compound with benzoyl chloride inaccordance with the general procedure described in Example 6.

Example 10 Example 11 Mono acetic ester of5-chloro-2-(2-iminopropanetriol-1,2,3) -1-nitrob enzene. This compoundcan be obtained by reacting 26 grams of 5-chloro-2-(2-iminopropanetriol-1,2,3) 1 nitrobenzene with 11 grams of aceticanhydride in accordance with the general procedure described in Example3. It has the formula:

CHzOC-CH; E angry-0:01:20]; o

CHQOH N02 Similarly in accordance with the general procedure describedhereinbefore the following compounds can be prepared:

l CHz-O-C-CH;

new. t O

i ll 11 i H G 1 I CHzOH H l a, o FGN-b-CH,

| dnzon N02 C1 sea. 6

butrra eiaud the hydrolyzed, as well as the unhydrolyzed mixed cellulosecarboxylic esters, such as cellulose acetate propionate and celluloseacetate butyrate, and the celluloseethers such as methyl cellulose,ethyl cellulose and benzyl cellulose.

The nitroaminobenzene ester compounds of our invention'ar'e, for themost part, relatively insoluble in water and, accordingly, they may beadvantageouslydirectly applied to the textile material undergoingcdloration in the form of an aqueous suspension which can be prepared bygrinding'the'dyeto a paste, in-the presence of a sulfonated oil, soap,or other suitable dispersing agent dispersing the resulting paste inWater. In I some instances, 1 the compounds may possess suflicientsolubility in water to render the use of a dispersing agent unnecessary.Generally speaking, however, the use of a dispersing agent is desirable.

Direct dyeing operations can, with advantage, be conducted attemperatures of about 75 to C., but any suitable temperature may beused. Thus, the textile material to be dyed or colored is ordinarilyadded to the dye bath at a temperature lower than that at which the mainportion of the dyeing is to be effected, a temperature of from 45 to 55C., for example, following which the temperature is raised to thatselected for carrying out the operation. The temperature at which thedyeing operation is carried out will vary somewhat depending upon theparticular material undergoing coloration. As is understood by thoseskilled in the art, the intensity of dyeing can be varied by varying theproportion of dye to the material undergoing coloration. Generallyspeaking, 1 to 3% by weight of dye to material is employed, although anydesired proportions can be used.

Suitable dispersing agents are disclosed in our United States Patent2,115,030, issued April 26, 1938. The process disclosed in this patentfor the dyeing of cellulose acetate can be used in applying the dyes ofthe present invention to cellulose acetate. While a satisfactory methodfor dyeing has been disclosed herein, it will be understood that anyother suitable methods for dyeing the non-vegetable textile materialsnamed herein can be employed. Lacquers may be colored with the dyecompounds of our invention by the methods customarily employed in thelacquer art.

We claim:

1. A compound having the general formula:

H YQN c:2-om t wherein Y represents a member selected from the groupconsisting of a chlorine atom and an N -ethyl sulfoneamide group and Rrepresents a member selected from the group consisting of a group.

2. The nitroaminobenzene compound having the formula:

11 12 3. The nitroaminobenzene compound having REFERENCES CITED theformula: The following references are of record in the H CHI-04143113file of this patent: Q -i- 5 UNITED STATES PATENTS N02 Number Name Date4. The nitroaminobenzene compound having 2338380 Hester et a1 theformula: OTHER REFERENCES H H oH, 0-( 3-0H3 10 Kremer et al., J. A. C.S., vol. 64 (1942), DD. GQH5NSQ N-(IJ CH2 0 1285-1286.

0 0 oHr-O-O-GH;

JAMES G. MCNALLY. JOSEPH B. DICKEY.

Certificate of Correction Patent No. 2,469,695. Ma e, 1949. JAMES G.McNALLY ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows:

Column 1, line 48, for that portion of the formula reading monocyelicbenzine read monocyclic benzene; column 4, line 52, Example 1, for aminoread imi'no;

column 6, lines 4 and 5, Example 4, for 2-(iminopropanediol-L3) read 7z-(z im'inopropqnediol-l ,8) column 11, line 11, claim 4, for thatportion of the formula read1ngNQ CH read N-O0H -t and that theeai'd'tters Patent should be readw ithfihese corrections therein that thesame may-co11f to the record of the case in the' Patent Office.

Signed and sealed this'lst day of November, A. D. 1949.

THOMAS F. Mihii HY,

Assistant Oommissioner of Patents.

